Sulfidation of iron confined in nitrogen-doped carbon nanotubes to prepare novel anode materials for lithium ion batteries
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摘要: 锂离子电池的性能高度依赖于负极材料的性能。由于商业石墨受限于较低的理论容量，开发新型炭材料和金属氧化物/硫化物引起越来越多的关注。黄铁矿（FeS2）具有较大理论储锂容量（894 mAh g-1），而且环保价廉。为了提高黄铁矿的电导率，改善其充/放电过程中的体积变化，合成了纳米碳管限域黄铁矿复合材料（FeS2/N-CNTs）。该材料基于填充有铁纳米线/棒的氮掺杂碳纳米管（Fe/N-CNTs）的独特结构，利用氮掺杂纳米碳管管壁上的缺陷，通过简易的硫化过程，实现了碳管内铁的原位限域硫化转化。所得FeS2/N-CNTs复合物中黄铁矿以两种形态存在，一种是由半开放的氮掺杂碳纳米管包裹的FeS2纳米线，另一种是FeS2纳米颗粒从管腔扩散并附着在碳管外壁上。FeS2/N-CNTs复合物作为锂离子电池的负极材料，表现出高放电容量（996 mAh g-1/0.1 A g-1）和良好的倍率性能，且循环性能优良。Abstract: The performance of lithium ion batteries (LIBs) is highly dependent on the properties of the anode materials. Developing new carbon materials and metal oxides/sulfides with high capacities has attracted growing attention due to the limited theoretical capacity of commercial graphite. Pyrite (FeS2) is environmental benign, inexpensive and has a high theoretical capacity of 894 mAh g-1 because of its four-electron reduction by lithium, which make it promising for use as an anode material of LIBs. To improve the electrical conductivity and volume change of pyrite, hybrids made of pyrite confined in nitrogen-doped carbon nanotubes (FeS2/N-CNTs) were fabricated by floating catalyst chemical vapor deposition (FCCVD), followed by sulfidation. Results indicate that the original Fe/N-CNTs formed during the FCCVD have iron nanowires or nanorods inside the N-CNTs and their sulfidation with sulfur vapor at 400℃ for 1, 2 and 5 h leads to FeS2/N-CNTs with pyrite contents of 22.4, 45.2, and 55.8 wt%, respectively. The pyrite in FeS2/N-CNTs is in two forms, one is FeS2 nanowires confined in half-open N-CNTs and the other is FeS2 nanoparticles attached to the outer walls of the N-CNTs as a result of diffusion out of the inner tubes. A large number of defects on the N-CNTs tube walls is necessary for the diffusion of sulfur vapor into the tubes to make the iron species accessible to the sulfur. The FeS2/N-CNTs-45.2 wt% has the highest discharge capacity (996 mAh g-1 at 0.1 A g-1), good rate capability and stable cycling performance as an anode material for LIBs.
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Key words:
- Lithium ion batteries /
- Carbon nanotubes /
- Nitrogen doping /
- Confinement /
- Sulfidation
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Tarascon J M, Armand M. Issues and challenges facing rechargeable lithium batteries[J]. Nature, 2001, 414:359-367. Roberts A D, Li X, Zhang H. Porous carbon spheres and monoliths:morphology control, pore size tuning and their applications as Li-ion battery anode materials[J]. Chemical Society Reviews, 2014, 43:4341-4356. Croguennec L, Palacin M R. Recent achievements on inorganic electrode materials for lithium-ion batteries[J]. Journal of the American Chemical Society, 2015, 137:3140-3156. Whittingham M S. Lithium batteries and cathode materials[J]. Chemical Reviews, 2004, 104:4271-4302. Sawai K, Iwakoshi Y, Ohzuku T. Carbon materials for lithium-ion (shuttlecock) cells[J]. Solid State Ionics, 1994, 69:273-283. Wu Z-S, Ren W, Xu L, et al. Doped graphene sheets as anode materials with superhigh rate and large capacity for lithium ion batteries[J]. ACS Nano, 2011, 5:5463-5471. Fan Z J, Yan J, Wei T, et al. Nanographene-constructed carbon nanofibers grown on graphene sheets by chemical vapor deposition:high-performance anode materials for lithium ion batteries[J]. ACS Nano, 2011, 5:2787-2794. De Las Casas C, Li W. A review of application of carbon nanotubes for lithium ion battery anode material[J]. Journal of Power Sources, 2012, 208:74-85. CHEN X-H, SONG H-H., YANG S-B. Preparation and electrochemical properties of nano-Si/C composites[J].New Carbon Materials, 2007:235-241. Poizot P, Laruelle S, Grugeon S, et al. Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries[J].Nature, 2000, 407:496-499. Wang Y, Li X, Zhang Y, et al. Ether based electrolyte improves the performance of CuFeS2 spike-like nanorods as a novel anode for lithium storage[J].Electrochimica Acta, 2015, 158:368-373. Ma W, Liu X, Lei X, et al. Micro/nano-structured FeS2 for high energy efficiency rechargeable Li-FeS2 battery[J]. Chemical Engineering Journal, 2018, 334:725-731. Yue G, Yan P, Fan X, et al. Structure and properties of cobalt disulfide nanowire arrays fabricated by electrodeposition[J].Electrochemical and solid-state letters, 2007, 10:D29-D31. Xu X, Meng Z, Zhu X, et al. Biomass carbon composited FeS2 as cathode materials for high-rate rechargeable lithium-ion battery[J]. Journal of Power Sources, 2018, 380:12-17. Li L, Caban-Acevedo M, Girard S N, et al. High-purity iron pyrite (FeS2) nanowires as high-capacity nanostructured cathodes for lithium-ion batteries[J].Nanoscale, 2014, 6:2112-2118. Tomczuk Z, Tani B, Otto N, et al. Phase relationships in positive electrodes of high temperature Li-Al/LiCl-KCl/FeS2 cells[J].Journal of the Electrochemical Society, 1982, 129:925-931. LI F F, LU W, NIU S Z, et al. Preparation and electrochemical performance of a graphene-wrapped carbon/sulphur composite cathode[J].New Carbon Materials, 2014, 4:309-315. XU Z, YOU H-H, ZHANG L, et al. Recent development of polysulfide barriers for Li-S batteries[J].New Carbon Materials, 2017:97-105. Peng H J, Huang J Q, Cheng X B, et al. Review on high-loading and high-energy lithium-sulfur batteries[J].Advanced Energy Materials, 2017. Wu B, Song H, Zhou J, et al. Iron sulfide-embedded carbon microsphere anode material with high-rate performance for lithium-ion batteries[J].Chem Commun (Camb), 2011, 47:8653-8655. Rui X, Tan H, Yan Q. Nanostructured metal sulfides for energy storage[J].Nanoscale, 2014, 6:9889-9924. Zhang D, Mai Y J, Xiang J Y, et al. FeS2/C composite as an anode for lithium ion batteries with enhanced reversible capacity[J].Journal of Power Sources, 2012, 217:229-235. Jun L, Yuren W, Yi W, et al. Carbon-encapsulated pyrite as stable and earth-abundant high energy cathode material for rechargeable lithium batteries[J].Advanced Materials, 2014, 26:6025-6030. Qiu W D, Xia J, Zhong H M, et al. L-cysteine-assisted synthesis of cubic pyrite/nitrogen-doped graphene composite as anode material for lithium-ion batteries[J].Electrochimica Acta, 2014, 137:197-205. Pan X, Bao X. Reactions over catalysts confined in carbon nanotubes[J].Chem Commun (Camb), 2008, 47:6271-6281. Chen W, Fan Z, Pan X, et al. Effect of confinement in carbon nanotubes on the activity of fischer-tropsch iron catalyst[J].Journal of the American Chemical Society, 2008, 130:9414-9419. Yang Z Q, Guo S J, Pan X L, et al. FeN nanoparticles confined in carbon nanotubes for CO hydrogenation[J].Energy & Environmental Science, 2011, 4:4500-4503. Xu L, Hu Y, Zhang H, et al. Confined synthesis of FeS2 nanoparticles encapsulated in carbon nanotube hybrids for ultrastable lithium-ion batteries[J].ACS Sustainable Chemistry & Engineering, 2016, 4:4251-4255. Smith B W, Luzzi D E. Formation mechanism of fullerene peapods and coaxial tubes:a path to large scale synthesis[J].Chemical Physics Letters, 2000, 321:169-174. Yu K-L, Zou J-J, Ben Y-H, et al. Synthesis of NiO-embedded carbon nanotubes using corona discharge enhanced chemical vapor deposition[J].Diamond and Related Materials, 2006, 15:1217-1222. Wang Z, Zhao Z, Qiu J. Carbon nanotube templated synthesis of CeF3 nanowires[J].Chemistry of Materials, 2007, 19:3364-3366. Chen W, Pan X, Bao X. Tuning of redox properties of iron and iron oxides via encapsulation within carbon nanotubes[J].Journal of the American Chemical Society, 2007, 129:7421-7426. Liu Y, Wang X, Dong Y, et al. Nitrogen-doped graphene nanoribbons for high-performance lithium ion batteries[J].Journal of Materials Chemistry A, 2014, 2:16832-16835. Hou J, Cao C, Idrees F, et al. Hierarchical porous nitrogen-doped carbon nanosheets derived from silk for ultrahigh-capacity battery anodes and supercapacitors[J].ACS nano, 2015, 9:2556-2564. Shao-Horn Y, Osmialowski S, Horn Q C. Reinvestigation of lithium reaction mechanisms in FeS2 pyrite at ambient temperature[J].Journal of the Electrochemical Society, 2002, 149:A1547-A1555. Golodnitsky D, Peled E. Pyrite as cathode insertion material in rechargeable lithium/composite polymer electrolyte batteries[J].Electrochimica Acta, 1999, 45:335-350. Xue H, Yu D Y W, Qing J, et al. Pyrite FeS2 microspheres wrapped by reduced graphene oxide as high-performance lithium-ion battery anodes[J].J Mater Chem A, 2015, 3:7945-7949. Luo J, Liu J, Zeng Z, et al. Three-dimensional graphene foam supported Fe3O4 lithium battery anodes with long cycle life and high rate capability[J].Nano Lett, 2013, 13:6136-6143. Liu Z, Lu T, Song T, et al. Structure-designed synthesis of FeS2@C yolk-shell nanoboxes as a high-performance anode for sodium-ion batteries[J].Energy Environ Sci, 2017, 10:1576-1580. Jia J, Hu X, Wen Z. Robust 3D network architectures of MnO nanoparticles bridged by ultrathin graphitic carbon for high-performance lithium-ion battery anodes[J]. Nano Research, 2017, 11:1135-1145. Zhang S, Zhu L, Song H, et al. Enhanced electrochemical performance of MnO nanowire/graphene composite during cycling as the anode material for lithium-ion batteries[J]. Nano Energy, 2014, 10:172-180. Tian W, Hu H, Wang Y, et al. Metal-organic frameworks mediated synthesis of one-dimensional molybdenum-based/carbon composites for enhanced lithium storage[J]. ACS nano, 2018, 12:1990-2000. Zhao C T, Yu C, Zhang M D, et al. Ultrafine MoO2-carbon microstructures enable ultralong-life power-type sodium ion storage by enhanced pseudocapacitance[J].Advanced Energy Materials, 2017, 7. -
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